JPS6345402B2 - - Google Patents
Info
- Publication number
- JPS6345402B2 JPS6345402B2 JP55029567A JP2956780A JPS6345402B2 JP S6345402 B2 JPS6345402 B2 JP S6345402B2 JP 55029567 A JP55029567 A JP 55029567A JP 2956780 A JP2956780 A JP 2956780A JP S6345402 B2 JPS6345402 B2 JP S6345402B2
- Authority
- JP
- Japan
- Prior art keywords
- crosslinked polystyrene
- polyethylene glycol
- polystyrene
- halomethylated
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000004793 Polystyrene Substances 0.000 claims description 33
- 229920002223 polystyrene Polymers 0.000 claims description 33
- 229920001223 polyethylene glycol Polymers 0.000 claims description 21
- 239000002202 Polyethylene glycol Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 8
- -1 polyoxyethylene groups Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- RBGOCSKFMWMTRZ-UHFFFAOYSA-M potassium picrate Chemical compound [K+].[O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O RBGOCSKFMWMTRZ-UHFFFAOYSA-M 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 description 2
- BEVWMRQFVUOPJT-UHFFFAOYSA-N 2,4-dimethyl-1,3-thiazole-5-carboxamide Chemical compound CC1=NC(C)=C(C(N)=O)S1 BEVWMRQFVUOPJT-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- DWANEFRJKWXRSG-UHFFFAOYSA-N 1,2-tetradecanediol Chemical compound CCCCCCCCCCCCC(O)CO DWANEFRJKWXRSG-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004970 halomethyl group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、ポリオキシエチレン基が架橋ポリス
チレンの分子鎖内または分子鎖間でエーテル結合
した架橋ポリスチレンの製造法に関するものであ
る。
本発明者等は、先に架橋ポリスチレンにポリエ
チレングリコールモノメチルエーテルを結合させ
た−CH2−Ｏ−（CH2CH2O）oCH3（ｎは３〜10の
整数を表わす。）基を有する架橋ポリスチレン、
および架橋ポリスチレンにポリエチレングリコー
ルを結合させた−CH2−Ｏ（CH2CH2O）pＨ（ｐは
３〜10の整数を表わす。）基を有する架橋ポリス
チレンは、相間移動触媒として（特開昭54−
63196号公報参照）、また液体クロマトグラフ用充
填剤として（特願昭54−27348号明細書参照）有
用であることを見出して提案している。
今般、本発明者等はこれらのオキシエチレン基
を有する架橋ポリスチレンの類縁化合物について
引き続き研究を進めた結果、ポリエチレングリコ
ールジアルコキシドとハロメチル化架橋ポリスチ
レンとを反応させると、ポリエチレングリコール
の両側の水酸基が架橋ポリスチレンと架橋ポリス
チレンの分子鎖内または分子鎖間でエーテル結合
したポリオキシエチレン基を有するポリマーが生
成し、該ポリマーがアルカリ金属イオンを選択的
に捕足しうることを見出し、本発明に到達した。
すなわち、本発明の要旨は、ハロメチル化架橋
ポリスチレンと、一般式（Ｉ）
XO（CH2CH2O）nＸ （Ｉ）
（式中、ｍは３〜10の整数を、Ｘはアルカリ金属
原子を表わす。）
で示されるポリエチレングリコールジアルコキシ
ドとを反応させることを特徴とする、ポリオキシ
エチレン基が架橋ポリスチレンの分子鎖内または
分子鎖間でエーテル結合した架橋ポリスチレンの
製造法に存する。
以下に本発明を詳細に説明する。
本発明方法の原料であるハロメチル化架橋ポリ
スチレンの架橋度は通常１％以上が好ましい。架
橋度が低すぎると、有機溶媒により膨潤するの
で、生成物の用途によつては好ましくない場合が
ある。
ハロメチル化架橋ポリスチレンは通常ジビニル
ベンゼンを架橋剤とするが、ジビニルトルエン、
ジビニルナフタレン等の芳香族ポリビニル化合物
およびジアクリル酸エチレングリコールエステ
ル、ジメタクリル酸エチレングリコールエステ
ル、アジピン酸ジビニル等の脂肪族ポリビニル化
合物等も架橋剤として挙げられる。
これらの架橋剤の量は、通常重合体中の１％
（重量）以上に相当する。
ハロメチル化架橋ポリスチレンは、この他にメ
チルスチレン、エチルスチレン、クロロスチレ
ン、クロロメチルスチレン等のモノビニル化合物
が少量共重合したものであつてもよい。
ハロメチル化架橋ポリスチレンは粒径が小さい
ことが好ましく、通常20メツシユ以下である。こ
のような架橋ポリスチレンは、ゲル型でも、ポー
ラス型でも、ハイポーラス型でもよい。
ハロメチル化架橋ポリスチレンは、例えば次の
ような方法により製造することができる。
すなわち、周知の方法によりスチレン等のモノ
ビニル化合物およびジビニルベンゼン等のポリビ
ニル化合物を水性媒体中で懸濁重合し、生成した
架橋ポリスチレンにクロロメチルメチルエーテル
を反応させるなどして、クロロメチル化架橋ポリ
スチレンを得る。この際、クロロメチル基が、ベ
ンゼン環の水素原子を、ベンゼン環１つあたり
0.1〜１置換しているようにする。
本発明方法の今一つの原料は、前記一般式
（Ｉ）で示されるポリエチレングリコールジアル
コキシドである。
一般式（Ｉ）において、Ｘはリチウム、ナトリ
ウム、カリウム、ルビジウム等のアルカリ金属原
子である。
一般式（Ｉ）において、ｍが２以下であると、
生成したポリオキシエチレン基が結合した架橋ポ
リスチレン（以下POE樹脂という）のアルカリ
金属イオン捕捉力が弱くて不満足であるし、また
ｍが10を越えるものは、ハロメチル化架橋ポリス
チレンと反応しにくい。ただし、ポリエチレング
リコール成分が分子量分布を有する混合物である
場合には、後述の実施例にも挙げるように、平均
分子量に相当するｍは10を越えても、その中の低
分子量のポリエチレングリコール成分が優先的に
反応するので、原料として用いることができる。
ポリエチレングリコールジアルコキシドは、常
法、例えばポリエチレングリコールをナトリウ
ム、カリウム等のアルカリ金属または水酸化ナト
リウム、水酸化カリウム等のアルカリ金属水酸化
物と反応させることにより製造できる。
ポリエチレングリコールジアルコキシドはハロ
メチル化架橋ポリスチレン中のハロメチル基に対
し、通常１〜20当量、好ましくは３〜10当量用い
る。
ポリエチレングリコールジアルコキシドの量が
少なすぎれば反応が不十分となるし、多すぎても
格別それに伴う効果がみられないので好ましくな
い。
反応は、通常、不活性溶媒中で行なう。このよ
うな不活性溶媒としては、例えばベンゼン、トル
エン、キシレン等の芳香族炭化水素等の非プロト
ン性不活性溶媒が挙げられる。不活性溶媒の量
は、ハロメチル化架橋ポリスチレン1gに対し、
５〜20ml程度用いる。
反応は、通常、窒素、ヘリウム等の不活性ガス
雰囲気下に行なう。
反応の際の温度は、通常、50〜200℃、好まし
くは80〜150℃程度である。この反応の時間は、
他の種々の条件により相違するが、通常１時間〜
１週間、好ましくは数日間程度である。
反応により製造されたPOE樹脂と未反応原料
を分離するには、原料の溶媒例えば水、メタノー
ル、エタノール等のアルコール、エチルエーテ
ル、イソプロピルエーテル、テトラヒドロフラ
ン、ジオキサン等のエーテル、アセトン、メチル
エチルケトン等のケトンなどで洗浄すればよい。
このようにして製造されたPOE樹脂は、模式
の構造式で
で示される様なポリオキシエチレン単位が架橋ポ
リスチレンの分子鎖内または分子鎖間でエーテル
結合したポリマー（POE樹脂）が得られる。
POE樹脂は、後述する参考例にも示した様に、
アルカリ金属イオン、アルカリ土類金属イオン、
アンモニウムイオン等の水溶液から、これらのイ
オンを選択的に捕捉する能力を有するので、非イ
オン性の金属イオン吸着樹脂として有用である
し、またその特性を利用して相間移動触媒や液体
クロマトグラフ用のカラム充填剤としても有用で
ある。
本発明方法は、このようなPOE樹脂を収率よ
く、穏和な条件で製造できる点で工業的価値の大
きなものである。
以下に実施例を挙げて、本発明を更に詳細に説
明するが、本発明はその要旨を超えない限り、以
下の実施例により限定を受けるものではない。
製造例 １
ポリエチレングリコールとしては、ヘプタエチ
レングリコール（以下EO7と略す）、粗デカエチ
レングリコール（以下EO10と略す）、粗ドデシル
エチレングリコール（以下EO12と略す、平均分
子量600のポリエチレングリコール混合物（以下
PEG600と略す）、ｍ＝13.5）、平均分子量1000の
ポリエチレングリコール混合物（以下PEG1000
と略す、ｍ＝22.3）を用いた。また比較のため、
ヘプタエチレングリコールモノメチル化物（以下
EO7Meと略す）も用いた。
ハロメチル化架橋ポリスチレンとしては、３％
のジビニルベンゼンで架橋したポリスチレンのベ
ンゼン環の水素原子を、クロロメチル基が、ベン
ゼン環１つあたり0.947置換したクロロメチル化
架橋ポリスチレン（以下Ａ樹脂という）を用い
た。
ポリエチレングリコールのアルコキシド化は、
ポリエチレングリコールに、カリウム、ナトリウ
ムまたは水酸化カリウムを加え、常法により行つ
た。
反応は、塩化カルシウム管を備えた窒素ガス吹
込管、塩化カルシウム管を備えた冷却器および温
度計を備えた三つ口フラスコを用い、表１に示し
た原料および反応条件で行い、反応後３規定塩
酸、ジオキサン−３規定塩酸（１：１）、ジオキ
サン−水、水、ジオキサン−水、ジオキサン、エ
タノール、エチルエーテルの順に洗い、含水（20
重量％）ジオキサンまたは含水（５重量％）テト
ラヒドロフランにより、ソツクスレー抽出器で48
時間洗浄した後、真空乾燥させて、収量を測定し
た。結果も表１に示した。
The present invention relates to a method for producing crosslinked polystyrene in which polyoxyethylene groups are ether bonded within or between molecular chains of crosslinked polystyrene. The present inventors have previously bonded polyethylene glycol monomethyl ether to crosslinked polystyrene, which has a -CH2 - O-( CH2CH2O ) oCH3 ( n represents an integer from 3 to 10) group. cross-linked polystyrene,
And crosslinked polystyrene having -CH 2 -O (CH 2 CH 2 O) p H (p represents an integer of 3 to 10) group, which is obtained by bonding polyethylene glycol to crosslinked polystyrene, is used as a phase transfer catalyst (Unexamined Japanese Patent Publication No. Showa 54-
63196) and as a packing material for liquid chromatography (see Japanese Patent Application No. 54-27348). Recently, the present inventors have continued to conduct research on compounds related to crosslinked polystyrene having these oxyethylene groups, and have found that when polyethylene glycol dialkoxide and halomethylated crosslinked polystyrene are reacted, the hydroxyl groups on both sides of polyethylene glycol are crosslinked. The present invention was achieved by discovering that a polymer having polyoxyethylene groups bonded within or between the molecular chains of polystyrene and crosslinked polystyrene is produced, and that this polymer can selectively capture alkali metal ions. That is, the gist of the present invention is to provide a halomethylated crosslinked polystyrene and a compound having the general formula (I) XO(CH 2 CH 2 O) n The present invention relates to a method for producing crosslinked polystyrene in which polyoxyethylene groups are ether bonded within or between the molecular chains of crosslinked polystyrene, characterized by reacting the polyethylene glycol dialkoxide represented by The present invention will be explained in detail below. The degree of crosslinking of the halomethylated crosslinked polystyrene, which is the raw material for the method of the present invention, is usually preferably 1% or more. If the degree of crosslinking is too low, the product will swell with organic solvents, which may be undesirable depending on the intended use of the product. Halomethylated crosslinked polystyrene usually uses divinylbenzene as a crosslinking agent, but divinyltoluene,
Aromatic polyvinyl compounds such as divinylnaphthalene and aliphatic polyvinyl compounds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and divinyl adipate are also mentioned as crosslinking agents. The amount of these crosslinking agents is usually 1% in the polymer.
(weight) or more. The halomethylated crosslinked polystyrene may also be one in which a small amount of a monovinyl compound such as methylstyrene, ethylstyrene, chlorostyrene, or chloromethylstyrene is copolymerized. The halomethylated crosslinked polystyrene preferably has a small particle size, usually 20 mesh or less. Such crosslinked polystyrene may be of gel type, porous type, or highly porous type. Halomethylated crosslinked polystyrene can be produced, for example, by the following method. That is, monovinyl compounds such as styrene and polyvinyl compounds such as divinylbenzene are suspension polymerized in an aqueous medium by a well-known method, and the resulting crosslinked polystyrene is reacted with chloromethyl methyl ether to produce chloromethylated crosslinked polystyrene. obtain. At this time, the chloromethyl group replaces the hydrogen atom of the benzene ring per benzene ring.
Make sure to replace 0.1 to 1. Another raw material for the method of the present invention is polyethylene glycol dialkoxide represented by the general formula (I). In general formula (I), X is an alkali metal atom such as lithium, sodium, potassium, rubidium, etc. In general formula (I), m is 2 or less,
The produced crosslinked polystyrene with polyoxyethylene groups bonded to it (hereinafter referred to as POE resin) has a weak and unsatisfactory ability to capture alkali metal ions, and those with m exceeding 10 are difficult to react with halomethylated crosslinked polystyrene. However, if the polyethylene glycol component is a mixture with a molecular weight distribution, as shown in the examples below, even if m, which corresponds to the average molecular weight, exceeds 10, the low molecular weight polyethylene glycol component in the mixture is Since it reacts preferentially, it can be used as a raw material. Polyethylene glycol dialkoxide can be produced by a conventional method, for example, by reacting polyethylene glycol with an alkali metal such as sodium or potassium or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The polyethylene glycol dialkoxide is usually used in an amount of 1 to 20 equivalents, preferably 3 to 10 equivalents, based on the halomethyl group in the halomethylated crosslinked polystyrene. If the amount of polyethylene glycol dialkoxide is too small, the reaction will be insufficient, and if it is too large, no particular effect will be seen, which is not preferable. The reaction is usually carried out in an inert solvent. Examples of such inert solvents include aprotic inert solvents such as aromatic hydrocarbons such as benzene, toluene, and xylene. The amount of inert solvent per 1 g of halomethylated cross-linked polystyrene is
Use about 5 to 20 ml. The reaction is usually carried out under an atmosphere of an inert gas such as nitrogen or helium. The temperature during the reaction is usually about 50 to 200°C, preferably about 80 to 150°C. The time for this reaction is
It varies depending on various other conditions, but usually 1 hour to
The period is about one week, preferably several days. In order to separate the POE resin produced by the reaction from unreacted raw materials, the raw material solvents such as water, alcohols such as methanol and ethanol, ethers such as ethyl ether, isopropyl ether, tetrahydrofuran and dioxane, and ketones such as acetone and methyl ethyl ketone are used. You can wash it with The POE resin produced in this way has a schematic structural formula: A polymer (POE resin) in which polyoxyethylene units are ether-bonded within or between the molecular chains of cross-linked polystyrene as shown in is obtained. As shown in the reference examples below, POE resin is
Alkali metal ions, alkaline earth metal ions,
Since it has the ability to selectively capture ammonium ions and other ions from aqueous solutions, it is useful as a nonionic metal ion adsorption resin, and its properties can also be used for phase transfer catalysts and liquid chromatographs. It is also useful as a column packing material. The method of the present invention has great industrial value in that it can produce such a POE resin in good yield under mild conditions. EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited by the Examples unless it exceeds the gist thereof. Production Example 1 Polyethylene glycols include heptaethylene glycol (hereinafter abbreviated as EO7), crude decaethylene glycol (hereinafter abbreviated as EO10), crude dodecylethylene glycol (hereinafter abbreviated as EO12), and a polyethylene glycol mixture with an average molecular weight of 600 (hereinafter abbreviated as EO12).
(abbreviated as PEG600), m=13.5), a polyethylene glycol mixture with an average molecular weight of 1000 (hereinafter referred to as PEG1000)
(abbreviated as m = 22.3) was used. Also, for comparison,
Heptaethylene glycol monomethylated compound (hereinafter referred to as
EO7Me) was also used. As halomethylated crosslinked polystyrene, 3%
Chloromethylated crosslinked polystyrene (hereinafter referred to as resin A) in which hydrogen atoms in the benzene rings of polystyrene crosslinked with divinylbenzene were substituted with 0.947 chloromethyl groups per benzene ring was used. Alkoxidation of polyethylene glycol is
Potassium, sodium or potassium hydroxide was added to polyethylene glycol and the test was carried out in a conventional manner. The reaction was carried out using a three-necked flask equipped with a nitrogen gas blowing tube equipped with a calcium chloride tube, a condenser equipped with a calcium chloride tube, and a thermometer, using the raw materials and reaction conditions shown in Table 1. Wash with normal hydrochloric acid, dioxane-3N hydrochloric acid (1:1), dioxane-water, water, dioxane-water, dioxane, ethanol, and ethyl ether in this order, and add water (20
48% by weight) dioxane or aqueous (5% by weight) tetrahydrofuran in a Soxhlet extractor.
After washing for a period of time, it was vacuum dried and the yield was measured. The results are also shown in Table 1.
【表】
度で反応させ、その後ろ過し、クロロホルムとア
セトンで洗い真空乾燥させた。
以上の結果から、PEG600、PEG1000、EO10、
EO12を用いた場合には、混在している低分子量
のポリエチレングリコールが優先的に反応してい
ることが分る。
参考例 １
POE樹脂による抽出能の測定
(i) ２×10-2M水酸化カリウム溶液とピクリン酸
溶液を等量混合し、ピクリン酸カリウム溶液と
する。POE樹脂0.2gを30mlの栓付マイヤーに精
秤し、上記のピクリン酸カリウム溶液をピペツ
トで10ml加える。2.5℃で表２に示した時間震
盪させた後、上澄液をろ紙でろ過した後、紫外
部吸光光度法で354nmの吸光度を測定し、定量
した。２回測定し、平均した。結果は表２に示
した。[Table] The reaction was carried out at 30°C, followed by filtration, washing with chloroform and acetone, and vacuum drying.
From the above results, PEG600, PEG1000, EO10,
It can be seen that when EO12 is used, the mixed low molecular weight polyethylene glycol reacts preferentially. Reference Example 1 Measurement of extractability using POE resin (i) Mix equal amounts of 2×10 -2 M potassium hydroxide solution and picric acid solution to obtain a potassium picrate solution. Precisely weigh 0.2 g of POE resin into a 30 ml Meijer with a stopper, and add 10 ml of the above potassium picrate solution with a pipette. After shaking at 2.5° C. for the time shown in Table 2, the supernatant liquid was filtered through filter paper, and the absorbance at 354 nm was measured by ultraviolet absorption spectrophotometry for quantitative determination. Measurements were taken twice and averaged. The results are shown in Table 2.
【表】
(ii) ピクリン酸の濃度を変えた５種のピクリン酸
溶液（14×10-5、14×10-4、5.6×10-3、1.2×
10-3、14×10-3M）と２×10-2M水酸化カリウ
ム溶液を等量混合し、ピクリン酸カリウム溶液
を調製した。その後(i)と同様にして24時間震盪
させ、樹脂AEO7−Ｋを用いて抽出能を測定し
た。結果は表３に示した。[Table] (ii) Five kinds of picric acid solutions with different concentrations of picric acid (14×10 -5 , 14×10 -4 , 5.6×10 -3 , 1.2×
10 -3 , 14×10 -3 M) and 2×10 -2 M potassium hydroxide solution were mixed in equal amounts to prepare a potassium picrate solution. Thereafter, the mixture was shaken for 24 hours in the same manner as in (i), and the extractability was measured using resin AEO7-K. The results are shown in Table 3.
【表】
(iii) アルカリ溶液として２×10-2Mの水酸化リチ
ウム、水酸化ナトリウム、水酸化カリウム、水
酸化ルビジウム、水酸化セシウム水溶液を用
い、ピクリン酸は1.4×10-4Mの溶液を用いて
(i)と同様に抽出能を測定した。（震盪は24時間）
結果は表４に示した。[Table] (iii) A 2×10 -2 M aqueous solution of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide was used as the alkaline solution, and a 1.4×10 -4 M solution of picric acid was used. Using
Extractability was measured in the same manner as in (i). (Shaking was carried out for 24 hours) The results are shown in Table 4.
【表】
表５には、ナトリウムとカリウムの分離能
（DK＋／DNa＋）を示した。[Table] Table 5 shows the separation ability for sodium and potassium (D K + /D Na +).
【表】
これらの結果から、POE樹脂は直鎖状のポリ
オキシエチレン基を有する架橋ポリスチレンより
も、金属イオンの抽出力、分離能ともに優れてい
ることが判る。
製造例 ２
製造例１において、ポリエチレングリコールと
して、平均分子量300のポリエチレングリコール
混合物（以下PEG300と略す、ｍ＝6.4）、ペンタ
エチレングリコール（以下EO5と略す）、ヘキサ
エチレングリコール（以下EO6と略す）に代え、
表６に示した製造条件とした他は同様に製造し
た。
また、比較のためデカエチレングリコールモノ
メチル化物（以下EO10Meと略す）を用いた。
結果を、表６に示した。[Table] From these results, it can be seen that POE resin is superior to crosslinked polystyrene having linear polyoxyethylene groups in both metal ion extraction power and separation ability. Production Example 2 In Production Example 1, a polyethylene glycol mixture with an average molecular weight of 300 (hereinafter abbreviated as PEG300, m = 6.4), pentaethylene glycol (hereinafter abbreviated as EO5), and hexaethylene glycol (hereinafter abbreviated as EO6) were used as polyethylene glycol. Instead,
It was manufactured in the same manner except that the manufacturing conditions shown in Table 6 were used. In addition, decaethylene glycol monomethylated product (hereinafter abbreviated as EO10Me) was used for comparison. The results are shown in Table 6.
【表】
参考例 ２
参考例１と同様にして、製造例２の生成物の抽
出能および分配係数を測定した。結果は表７に示
した。[Table] Reference Example 2 In the same manner as Reference Example 1, the extractability and partition coefficient of the product of Production Example 2 were measured. The results are shown in Table 7.
【表】
以上の結果を総合し、Na+を1.00とした分離係
数（α）を表８に、Li＋を1.00とした分離係数
（α）を表９に示した。[Table] Combining the above results, Table 8 shows the separation coefficient (α) when Na + is 1.00, and Table 9 shows the separation coefficient (α) when Li + is 1.00.
【表】【table】
【表】【table】
【表】
代表的なPOE樹脂の分子鎖内、分子鎖間反応
による環化割合を、元素分析（Ｃ％）より求めた
ものおよび３，５−ジニトロベンゾイル化した後
のＮ（％）より求めたものを表10にまとめた。[Table] The cyclization ratio due to intramolecular chain and intermolecular chain reactions of typical POE resins was determined from elemental analysis (C%) and N after 3,5-dinitrobenzoylation (%). The results are summarized in Table 10.
Claims (1)
（Ｉ） XO（CH2CH2O）mX （Ｉ） （式中、ｍは３〜10の整数を、Ｘはアルカリ金属
原子を表わす。） で示されるポリエチレングリコールジアルコキシ
ドとを反応させることを特徴とする、ポリオキシ
エチレン基が架橋ポリスチレンの分子鎖内または
分子鎖間でエーテル結合した架橋ポリスチレンの
製造法。[Claims] 1 Halomethylated cross-linked polystyrene and general formula (I) XO(CH 2 CH 2 O) m .) A method for producing crosslinked polystyrene in which polyoxyethylene groups are ether-bonded within or between the molecular chains of crosslinked polystyrene, the method comprising reacting the polyethylene glycol dialkoxide shown in the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2956780A JPS56125402A (en) | 1980-03-08 | 1980-03-08 | Production of crosslinked polystyrene having bonded polyoxyethylene group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2956780A JPS56125402A (en) | 1980-03-08 | 1980-03-08 | Production of crosslinked polystyrene having bonded polyoxyethylene group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56125402A JPS56125402A (en) | 1981-10-01 |
| JPS6345402B2 true JPS6345402B2 (en) | 1988-09-09 |
Family
ID=12279697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2956780A Granted JPS56125402A (en) | 1980-03-08 | 1980-03-08 | Production of crosslinked polystyrene having bonded polyoxyethylene group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56125402A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE9902133D0 (en) * | 1999-06-06 | 1999-06-06 | Amersham Pharm Biotech Ab | A method for surface modification, a novel support matrix and the use of the matrix |
| JP4929635B2 (en) * | 2005-07-14 | 2012-05-09 | 富士ゼロックス株式会社 | Maleimide group-containing porous crosslinked polystyrene particles and method for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5379986A (en) * | 1976-12-24 | 1978-07-14 | Kuraray Co Ltd | Novel polymer |
-
1980
- 1980-03-08 JP JP2956780A patent/JPS56125402A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5379986A (en) * | 1976-12-24 | 1978-07-14 | Kuraray Co Ltd | Novel polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56125402A (en) | 1981-10-01 |
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